Optical terpolymer of polyisocyanate, polythiol and polyene monomers

ABSTRACT

A monomer composition characterized by being curable to form a resin suitable for optical products having a balanced refractive index and Abbe&#39;s number range and good tintability comprising a polyene monomer; and polyisocyanate, polyisothiocyanate, or an isocyanate monomer containing at least one isothiocyanate group; and a monomer having two or more active hydrogen groups such as polythiols, polyamines, and polyols. The invention also provides a special process for making the composition and for curing the composition to form a resin product.

This is a continuation of application Ser. No. 08/425,958 filed on Apr.19, 1995 now U.S. Pat. No. 6,008,296.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to optic polymers and, in particular, to opticalpolymers prepared by reacting a polyene monomer, a polyisocyanate orpolyisothiocyanate monomer and a monomer having at least two activehydrogen groups, and to a process for preparing such polymers and tooptic products made from such polymers.

2. Description of Related Art

Polymeric materials are used extensively as substitutes for glass inoptical products such as lenses. The use of polymeric materials overglass offers several practical advantages. Since polymeric materialshave a lower density than inorganic glass, there can be a greatreduction in weight of the optical product.

Additionally polymeric materials may offer great improvement over glassin terms of impact resistance. The improved processability and othercharacteristics such as tintability make polymeric materials especiallyattractive as a material for ophthalmic lenses. A variety of polymericmaterials including polycarbonates, polystyrenes, acrylic polymers,polythiourethane, and polysulfones have already been used for opticalapplications. Each of these materials offers a somewhat differentcombination of physical and optical properties which lead to advantagesand disadvantages for optical applications. For example, polycarbonatelenses typically show excellent impact resistance but are alsocharacterized by poor scratch resistance and tintability and highchromatic aberration. Acrylic polymers have excellent optical clarity,but poor impact resistance and a relatively low refractive index.Polystyrenes are typically characterized by a relatively high refractiveindex, but also show a great deal of optical dispersion combined withpoor impact resistance. Polysulfones have a high refractive index, butare typically colored and typically difficult to process.

Considerable research has been directed towards development of polymerswith a combination of properties which make them well suited for opticalapplications. Generally, a high refractive index is of principalimportance for an optical material since the use of a high refractiveindex material allows for production of thinner lenses when designinglenses of the same power and design. Reduction of edge thickness of thelens offers practical advantages in terms of weight savings andaesthetic reasons. Another important consideration for optical materialsis optical dispersiveness. The value of optical dispersiveness istypically characterized by the Abbe's number. Materials with high Abbenumbers show little optical dispersiveness while materials with low Abbenumbers show high optical dispersiveness. A high Abbe number is desiredfor optical materials since this will lead to reduced chromaticaberration and better image clarity for a given lens design andthickness. Typically polymers with high refractive indices also possesslow Abbe numbers. An Abbe number close to 40 is 20 considered to be highenough for desired eyeglass application. The two most common plasticlenses in the market, polycarbonate and CR-39 lenses, have shortcomingsin optical properties. Polycarbonate lenses, for instance, have arelatively high refractive index of 1.59 and a relatively low Abbenumber of 30.4. Lenses made of diethylene glycol bis(allylcarbonate)(CR-39 resin) have a low refractive index of 1.49 and an Abbenumber of 58. Therefore, when using an optical material, it is veryimportant to balance refractive index and Abbe number so that both aresuitable for the end product. Optimally, both refractive index and Abbenumber should be high.

Several other considerations are of importance for optical materials,especially for use in ophthalmic lenses. Tintability and impactresistance have both become especially important properties forophthalmic lens materials. Polycarbonate lenses are known for theirexcellent impact resistance; however, polycarbonate is extremelydifficult to tint. Polythiourethane lenses may also possess good impactresistance, but elevated temperatures are required for tinting which maylead to possible lens deformation. Therefore polymers having improvedtintability properties over these optical polymers is desired.

Weathering stability is another problem for most plastic lenses,especially for polythiourethane based lenses. Free —SH groups at the endof the polythiourethane polymeric molecules are readily oxidized byoxygen over a period of time or at elevated temperature and the lenseswill become yellow. It is also the intention of the invention to reduceor eliminate free SH groups to enhance the weathering stability.Additionally, properties such as optical clarity and transmittance,coloration, hardness, machinability, processability and the like mustalso meet certain property levels in optical materials useful for use inoptical products.

A number of patents have been granted directed to optical resins.

U.S. Pat. No. 4,689,387 is directed to a S-alkyl thiocarbamate base lensresin obtained by reacting one or more —NCO containing compounds withone or more —SH containing aliphatic compounds. The patent disclosesusing a radical-polymerizable raw material in the reaction in smallamounts depending what requirements would be imposed as a lens resin, solong as these additional components do not prevent the attainment of theobject of the subject invention. Radical-polymerizable raw materialssuch as diethylene glycol bis (allyl carbonate) (DAC), an acrylic ester,a methacrylic ester or a styrene derivative along with its radicalpolymerization initiator may be used in small amounts in the reactionmixture.

U.S. Pat. No. 4,775,733 claims a high-refractivity plastic lens resinconsisting essentially of a polymeric reaction product obtained bycopolymerizing a polyisocyanate with a polythiol.

U.S. Pat. No. 4,780,522 claims an optical lens comprising a copolymerobtained by reacting an isocyanate with an —OH containing compoundhaving two or more —OH groups.

U.S. Pat. No. 4,946,923 claims an S-alkyl thiocarbonate base resin 5comprising reacting a polyisocyanate with at least onehydroxyl-containing mercapto compound.

U.S. Pat. No. 5,084,545 claims a plastic lens comprising the reactionproduct of one or more isothiocyanate compounds with one or more polyol,polythiol, or polythiol-hydroxy compounds.

U.S. Pat. No. 5,310,847 claims a polyurethane composition suitable foroptical lenses which is made by reacting a polyisocyanate free ofintermolecular sulfur atoms and an acylic saturated monomer having atleast three reactive groups with respect to isocyanates per molecule.The reactive groups may be mercapto.

U.S. Pat. No. 5,047,576 is directed to a polymerizable vinyl compoundhaving a polythioether skeleton, which is prepared by addition-reactionof a polyene compound which is a specifically defined acryloyl oracryloyl amide having an aliphatic or alicyclic residue with at leastone (1) polythiol compound in the presence of a basic catalyst.

U.S. Pat. No. 5,270,439 is directed to a method of producing a curablecomposition containing: 1.) a prepolymer having a polythioether skeletonmade by addition reacting 4,4′-bis(methacryloythio) diphenylsulfide anda polythiol having the formula R—(SH)_(m) and 2.) at least one othervinyl monomer being copolymerizeable with the 4,4′compound in thepresence of a base catalyst.

U.S. Pat. No. 5,352,757 claims sulfur compounds of the general formula[HS—R₁—COO]—_(n)A where R₁ is a linear or branched alkylene radicalcontaining one to three carbon atoms and A denotes a hydrocarbon residueof valency n chosen from four particular aromatic and cycloaliphaticradicals. The sulfur compounds are used in the preparation ofpolythiourethanes by reaction of the sulfur compound and an aromaticpolyisocyanate. The sulfur compounds are also employed for preparingpolythioethers by reaction with a polyene monomer. Both thepolyurethanes and polythioethers obtained from the subject sulfurcompounds have properties which enable them to be employed in optics. Itis also disclosed that the polythiourethane and polythioether polymersformed may be used alone or mixed for optical purposes such as themanufacture of ophthalmic lenses.

U.S. Pat. No. 4,120,721 is related to a liquid radiation curablecomposition useful for coating and imaging which comprises: 1.) anacrylic or methacrylic terminated, urethane containing polyene, 2.) anon-water soluble vinyl monomer diluent, preferably an acrylate ormethacrylate monomer diluent, 3.) a polythiol containing at least twothiol groups per molecule and 4.) a photoinitiator. The composition onexposure to radiation, e.g., a UV light source, cures to a solidpolythioether.

Bearing in mind the problems and deficiencies of the prior art, it isaccordingly an object of the present invention to provide polymerizablemonomeric compositions and polymeric materials having a combination ofproperties which are superior in many aspects to that of existingoptical materials. It is another object of the present invention toprovide a process for preparing optical resins having a superiorcombination of physical and optical properties. The terpolymer systemdescribed herein offers advantages over poythiourethane homopolymers inthat the terpolymers have reduced yellowness, enhanced tintability andweathering stability, as well as a reduced odor in the uncured resin.The terpolymer system offers advantages over polythioether homopolymersystems in terms of enhanced impact resistance and an enhancedrefractive index and Abbe number combination.

Still other objects and advantages of the invention will in part beobvious and will in part be apparent from the specification.

SUMMARY OF THE INVENTION

In this invention, it has been discovered that reacting effectiveamounts of polythiols with both polyenes, preferably with three (3) orhigher number of vinyl groups in the monomers, and polyisocyanatesresults in a new class of terpolymers which are homogeneous systemswithout any significant phase separation and have enhanced propertiesfor optical applications such as eyeglasses. Among these properties area balanced high refractive index and high Abbe number, enhancedtintability and enhanced weathering stability and good impactresistance. The subject of this invention are optical resins having acombination of high refractive index and high Abbe number produced fromcurable or thermoplastic monomer compositions. The monomer compositionis comprised of a polyene monomer, a polyisocyanate orpolyisothiocyanate monomer or a polyisocyanate monomer containing atleast one isothiocyanate group and a monomer having two or more activehydrogen groups such as hydroxy, thiol, NH, NH₂ or mixtures thereof. Bypolyene monomer is meant a compound containing two or more vinyl groups.For convenience, the term polyisocyanate will be meant to includepolyisocyanate, polyisothiocyanate, and polyisocyanate monomerscontaining at least one isothiocyanate group, or mixtures thereof.

A preferred polymer is formed by the reaction of a polyacrylate orpolymethacrylate monomer, a polyisocyanate monomer and a polythiolmonomer. Preferred monomers because of their demonstrated utility arepentaerythritol tetraacrylate, m-xylylene diisocyanate, pentaerythritoltetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 2-mercaptoethyl sulfide and 1,2-ethanedithiol.Another polyene which is preferred istriallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-5trione.

In another aspect of the invention, a process is provided for preparingoptical resin products with enhanced optical and physical propertiesfrom the composition comprising a polyene monomer, polyisocyanatemonomer and active hydrogen groups containing monomer. Broadly stated,the process comprises preparing a mixture of the polyene monomer andpolyisocyanate monomer under non-reactive conditions and cooling themixture to a temperature, for example, less than about 15° C. Adding thehydrogen group containing monomer, or mixture of such monomers, whichare separately mixed under non-reactive conditions and cooled to atemperature, for example, below about 15° C., to thepolyene-polyisocyanate mixture and maintaining the temperature belowreaction conditions, e.g., below abut 15° C. An initiator is added forinitiating the reaction and the mixture preferably degassed. The mixtureis kept cool, e.g., at a temperature below about 15° C. for up to 72hours, preferably 10 to 32 hours and is then cast (cured) at an elevatedtemperature to produce the optical resin of the invention. A preferredcuring process is also disclosed.

In another aspect of the invention, the optical resin products may beprepared by casting or other mold type polymerization process to producea cross-linked resin optical product. The resin can also be formed as alinear thermoplastic polymer which polymer can then be injection moldedor compression molded into optical and other products at high productionrates.

As distinct from the prior art aforementioned, this invention does notuse a small amount of radical polymerizable raw materials as additivesin polythiourethane homopolymer systems, especially monomers with onlyone vinyl group such as styrenes, acrylic esters, methacrylic esters,because incorporation of these monomers in thiourethane systems willseverely deteriorate mechanical, as well as optical properties of theresultant material which is not suitable for lens application withcommercial value.

DESCRIPTION OF THE PREFERRED EMBODIMENT(S)

Any suitable compound selected from polyisocyanate compounds,polyisothiocyanate compounds and isocyanate-group-containing compoundscontaining at least one isothiocyanate group may be employed.

The polyisocyanate monomers may be defined by the general formula

R(NCY)_(x)  (I)

wherein x is two or more Y is O or S, R can be alklylene, arylene,hydrocarbon or substituted hydrocarbon containing one or more aryl-NCYbonds and/or one or more alkyl-NCY bonds. R can also include radicalssuch as —R—Z—R where Z may be any divalent moiety such as O, CO, CO₂, S,SRS, ORO, SO₂, etc.

In the present invention, one or more NCO-containing compoundscontaining two or more isocyanate groups (NCO groups) can be used. Thesecompounds are generally termed polyisocyanates and may be eitheraromatic, aliphatic or cycloaliphatic. Aromatic compounds may benucleus-substituted, by one or more halogens and/or the like. Exemplarypolyisocyanate compounds include m-xylylene diisocyanate, p-xylylenediisocyanate, hexamethylene diisocyanate, isophorone diisocyanate,toluene diisocyanate, 4,4′-diphenylmethane diisocyanate, the biuretreaction product of hexamethylene diisocyanate, the adduct reactionproduct of hexamethylene diisocyanate and trimethylolpropane,4,4′-dichlorohexylmethane diisocyanate and 2-isocyanatoethyl2,6-diisocyanatohexanoate. Preferred polyisocyanate monomers are thearomatic diisocyanates, in each of which two side-chain alkyl groupshave been substituted by two NCO groups, such as m-xylylenediisocyanate.

Aliphatic diisocyanates such as hexamethylene diisocyanate and 1,3-bis(isocyanato-methyl)cyclohexane are also preferred because they arecommercially available.

The polyisothiocyanate monomer employed in this invention is a compoundcontaining two or more —NCS groups in a molecule and, optionally, one ormore sulfur atoms in addition to the isothiocyanate groups. Specificexamples include aliphatic polyisothiocyanates such as1,2-diisothiocyanatoethane, 1,3-diisothiocyanatopropane, andp-phenylenediisopropylene diisothiocyanate; alicyclicpolyisothiocyanates such as 1,2-diisothiocyanatobenzene,2,4-diisothiocyanatotoluene, 2,5-diisothiocyanato-m-xylene, and4,4′-diisothiocyanato 1,1′-biphenyl.

Exemplary isothiocyanate compounds, which contain an isocyanato groupand are usable in this invention include aliphatic or alicycliccompounds such as 1-isocyanato-3-isothiocyanatopropane,1-isocyanato-5-isothiocyanatopentane,1-isocyanato-6-isothiocyanatohexane, isothiocyanatocarbonyl isocyanate,and 1-isocyanato-4-isothiocyanatocyclohexane; aromatic compounds such as1-isocyanato-4-isothiocyanatobenzene and4-methyl-3-isocyanato-1-isothiocyanatobenzene; heterocyclic compoundssuch as 2-isocyanato-4,6-diisothiocyanato1,3,5-triazine; and compoundscontaining one or more sulfur atoms in addition to an isothiocyanatogroup, such as 4-isocyanato-4′isothiocyanatodiphenyl sulfide and2-isocyanato-2′isothiocyanatodiethyl disulfide.

The NCO and NCS compounds include their halogen-substituted derivatives,such as chlorine-substituted derivatives and bromine-substitutedderivatives, alkyl-substituted derivatives, alkoxy-substitutedderivatives, nitrosubstituted derivatives, prepolymer-type derivativesmodified with polyhydric alcohols, carbodiimide modified derivatives,urea-modified derivatives, biuret-modified derivatives, dimerizedreaction products, trimerized reaction products, and the like. The NCOand NCS isocyanate and isothiocyanate compound can be used either singlyor in combination.

Any suitable polyene monomer may be used and may be selected from a widevariety of known monomers. The polyene monomer is meant to be a monomercontaining at least two and preferably three, four or more vinyl groups.One class of polyene monomers may be represented by the formula (II):

[CH₂═CR₁—CO—A]_(y)—R₂  (II)

where in R₂ is a polyvalent aliphatic or alicyclic and aromatichydrocarbon residue, R₁ is H or CH₃, A is oxygen, sulfur or —NH and y is2-6.

Typical examples of polyene monomers are ethylene glycol diacrylate ordimethacrylate, diethylene glycol diacrylate or dimethacrylate,triethylene glycol diacrylate or dimethacrylate tetraethylene glycoldiacrylate or dimethacrylate, 2-hydroxypropyl-1,3-diacrylate ordimethacrylate, 1,6-hexane-diacrylate or -dimethacrylate, neopentylglycol diacrylate or dimethacrylate, pentaerythritol triacrylate ortrimethacrylate, pentaerythritol tetraacrylate or tetramethacrylate,trimethylolpropane triacrylate or trimethacrylate, dipentaerythritolhexaacrylate or hexamethacrylate; amides such as ethylene diacrylamideor dimethacrylamide, 1,6-hexane diacrylamide or dimethacrylamide, propyldiacrylamide or dimethacrylamide, 1,4-cyclohexane diacrylamide ordimethacrylamide and bis(4-aminocyclohexyl)methane diacrylamide ordimethacrylamide; ethylene glycol dithioacrylate or dithiomethacrylate.Other polyenes include 1,4-(β-acryloyloxyethoxy or-methacryloyloxyethxy)cyclohexane. The polyenes may be used singly or incombination as a mixture.

Any suitable organic compound containing at least two active hydrogencontaining groups as determined by the Zerewitinoff method, e.g., saidgroups being reactive with an isocyanate group, may be used in theprocess of the present invention. The active hydrogen atoms are usuallyattached to oxygen, nitrogen or sulfur atoms. Thus, suitable activehydrogen containing groups as determined by the Zerewitinoff methodinclude OH, —NH₂, —NH—, —COOH, —SH and the like. Examples of suitabletypes of organic compounds containing at least two active hydrogencontaining groups are polyhydric polyalkylene ethers, polyhydricpolythioethers, polyacetals, aliphatic polyols, including alkane, alkeneand alkyne diols, triols, tetrols and the like; aliphatic thiolsincluding alkane, alkene and alkyne thiols having two ore more —SHgroups; polyamines including aromatic, aliphatic and heterocyclicdiamines, triamines, tetramines and the like; polyaralkylene ethers suchas propylene oxide and ethylene oxide adducts of resorcinol,hydroquionone, bisphenol-A and the like, as well as mixtures thereof.Compounds which contain two or more different groups within theabove-defined classes may also be used in accordance with the process ofthe present invention, such as an amino group and one hydroxyl group andthe like. Also, compounds may be used which contain one —SH group andone —OH or two —OH groups and one —SH group as well as those whichcontain an amino group and an —SH group and the like. When compoundscontaining only —OH groups are used, they have to be used in combinationwith —SH group-containing compounds. The ratio of —OH and —SH in themixture is preferably in the range of —OH/—SH 0.1-5.

Exemplary active hydrogen monomers may be represented by the followinggeneral formulae (III) and (IV):

HA—R₃—(BH)_(z)  (III)

wherein R₃ is an organic group consisting of polyvalent aliphatic oralicyclic hydrocarbon preferably having 2 to 10 carbon atoms, z is aninteger of from 1 to 3, and B is O, S or NH; and

wherein R₄ is a substituted or unsubstituted aliphatic polyhydricalcohol residue having 2 to 20 carbon atoms, which may have an OH group,u is an integer of 1 or 2, and v is an integer of from 2 to 4.

Typical examples of polythiol compounds represented by the generalformula (III) where A is sulfur include 1,2-ethanedithiol,propane-1,2-dithiol, n-hexane 1,6-dithiol, n-decane-1,10-dithiol,n-dodecane-1,12-dithiol, 1,3-cyclohexanedithol and1,4-cyclohexanedithol.

As typical examples of the polythiol compound represented by the generalformula (IV), there can be mentioned ethylene glycol dithioglycolate,diethylene glycol dithioglycolate, trimethylolpropane trithioglycolate,trimethylolpropane dithioglycolate, neopentylglycol tetrathioglycolate,pentaerythritol tetrathioglycolate, trimethylolpropane trithiopropionateand pentaerythritol tetrakis(2-mercaptoacetate).

Other exemplary suitable polythiols for use in the process of theinvention include aliphatic polythiols such as 1,1-propanedithiol,1,2,3-propanetrithiol, diethylene glycol bis(2-mercaptoacetate),1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether,2,2-bis(mercaptomethyl)-1,3-propanedithiol, bis(2-mercaptoethyl) ether,ethylene glycol bis (2-mercaptoacetate), trimethylolpropanebis(2-mercaptoacetate), trimethylolpropane bis (3-mercaptopropionate),and pentaerythritol tetrakis(3-mercaptopropionate); aromatic polythiolssuch as 1,2-dimercaptobenzene, 1,3-dimercaptobenzene,1,4-dimercaptobenzene, aromatic polythiols containing sulfur atoms inaddition to mercapto groups such as 1,2-bis(mercaptomethylthio)benzene,and aromatic ring alkylated derivatives of these polythiols.

Aliphatic thiols containing sulfur atoms in addition to mercapto groupssuch as bis(mercaptomethyl) sulfide and bis (3-mercaptopropyl)methaneand 1,2-bis(mercaptomethylthio)ethane may be employed.

Exemplary polyol compounds include aliphatic polyols such as ethyleneglycol, diethylene glycol, propylene glycol, glycerol,trimethylolethane, trimethylolpropane, butanetriol, pentaerythritol,dipentaerythritol, tripentaerythritol, sorbitol, erythritol, triethyleneglycol, polyethylene glycol, tris(2-hydroxyethyl)isocyanurate,cyclobutanediol, cyclopentanediol, cyclohexanediol, cyclohexanetriol,maltitol, lactitol; aromatic polyols such as dihydroxynaphthalene,trihydroxynaphthalene, tetrahydroxynaphthalene, hydroquinone,resorcinol, catechol, benzenetriol, biphenyltetraol, bisphenol A-,bisphenol F, xylyleneglycol, di(2-hydroxyethoxy) benzene, bisphenolA-bis(2-hydroxyethylether), tetrabromobisphenol-A, tetrabromobisphenolA-bis(2-hydroxyethylether); and high molecular polyols such as epoxyresin.

Additional exemplary polyols include condensed products of abovementioned polyol compounds with organic acids such as oxalic acid,glutamic acid, adipic acid, acetic acid and propionic acid; additionproducts of alkylene oxides such as ethylene oxide and propylene oxideto the above polyol compounds and to alkylenepolyamine; and sulfur atomcontaining polyols such as bis[4-(hydroxyethoxy)phenyl]sulfide,compounds obtained by the addition of ethylene oxide and/or propyleneoxide to sulfur containing polyols.

Exemplary suitable mercapto group containing hydroxy compounds for usein the process of this invention include mercaptoalkanols,mercaptocycloalkanols and mercapto phenols such as 2-mercaptoethanol,3-mercapto1,2-propanediol, glycerol di(mercaptoacetate),1-hydroxy4-mercaptocyclohexane, 2,4-dimercaptophenol,2-mercaptohydroquinone, 4-25mercaptophenol, 3,4-dimercapto-2-propanol,1,3-dimercapto-2-propanol, 2,3-dimercapto-1-propanol,1,2-dimercapto-1,3-butanediol, pentaerythritoltris(3-mercaptopropionate), pentaerythritol bis(3-mercaptopropionate),pentaerythritol tris (thioglycolate), pentaerythritoltetrakis(3-mercaptopropionate), and mercapto group and sulfur atomcontaining alkanols and phenols such ashydroxymethyltris(mercaptoethylthiomethyl)methane,1-hydroxyethylthio-3-mercaptoethylthiobenzene,4-hydroxy-4′-mercatodiphenylsulfone, 2-(2-mercaptoethylthio)ethanol,dihydroxyethyl sulfide mono (3-mercaptopropionate), dimercaptoethanemonosalicylate, andhydroxyethylthiomethyl-tris(mercaptoethylthiomethyl)methane.

Halogenated derivatives of all aformentioned active-hydrogen containingcompounds such as chlorinated derivatives and brominated derivatives mayalso be used.

The active-hydrogen containing compounds may be used singly or incombination as a mixture.

The monomers may be used in widely varying amounts depending on theresin properties and optic product properties desired. In general, thecurable composition comprises, by weight, polyisocyanate monomer in anamount of about 2 to 70%, preferably 10 to 30%; polyene monomer in anamount of about 5 to 70%, preferably 10 to 40%; and an active hydrogencontaining monomer in an amount of about 10 to 60%, preferably 20 to50%. Higher or lower amounts may be employed for certain applications.

The proportions of the monomers may likewise range widely depending onthe polymer properties desired. In general, the ratio of the NCO/NCSgroups to the active hydrogen containing groups is about 0.05 to 0.9preferably 0.2 to 0.8. The ratio of vinyl groups to active hydrogencontaining groups is about 0.1 to 0.95, preferably 0.2 to 0.7. The ratioof NCO or NCS groups and vinyl groups to —SH group (—NCO orNCS+vinyl)/—SH is preferably in the range of 1.05 to 2.0. This ratiowill ensure reduction of free-SH groups in the end product. Therefore itwill enhance weathering stability of the end product.

The optical resins and products of this invention may be produced bycasting polymerization. Any one of molds and frames of various shapesdesigned in accordance with individual end uses, such as plate-like,lens-like, cylinder-like, prismatic, conical, aspherical, progressive,bifocal and spherical shapes may be used as a casting polymerizationvessel. The mold material is any suitable material such as inorganicglass, a plastic or a metal. The polymerization reaction is effectedgenerally by pouring a mixture of the monomer composition and apolymerization initiator into a casting polymerization vessel and ifnecessary, heating the contents. It is also feasible to conduct thepolymerization to a certain extent in a separate polymerization vessel,pouring the resultant prepolymer or syrup into a casting polymerizationvessel and then bringing the polymerization reaction to completion. Thecomposition of the invention has been found to have excellent castingproperties since the composition does not significantly react with thegasketing material which is usually rubber.

The monomer composition to be subjected to a polymerization reaction canalso contain conventional additives such as an antistatic agent, a heatstabilizer, an ultraviolet absorbent, an antioxidant, dyes and/or one ofmore other auxiliary additives in accordance with the intended end useof the terpolymer to be formed.

The terpolymer product may be subjected to a post treatment such asheating or annealing for completing the polymerization, for enhancingthe surface hardness, for eliminating strain accumulated internally uponthe casting polymerization, or for other purposes.

Secondary lens processing can also be applied to optical productsobtained from the optical material according to this invention. Forexample, the optical products may be coated with a silica, titania,and/or zirconia-based hard coating material or an organic hard coatingmaterial of the ultraviolet curable type so as to form a hard surfacelayer, whereby the surface hardness is enhanced. It is possible to coatthe lenses by the process described herein with a monolayer ormultilayer antireflective coating of metal oxides, metal fluorides, orother such materials deposited through vacuum evaporation, sputtering,or some other method.

The optical materials provided by this invention may also be madephotochromic through incorporation of naphopyran compounds, spirocompounds, indoline compounds, and/or other such photochromic materials.The forementioned photochromic materials may be incorporated into theenhanced optical materials disclosed in this patent through tinting,mixing with monomer components before or during polymerization, thermaltransfer, or some other such technique. European patent application88304403.4 discusses improved fatigue resistance for reversible cleavagephotochromics when incorporated into polyurethane plastics, especiallythermosetting polyurethanes. The present invention offers severaladvantages over polyurethanes or polythiourethanes for use inphotochromic optical products. First, the terpolymer discussed in thisinvention offers all of the advantages of polyurethanes andpolythiourethanes for reducing fatigue through the reduction ofirreversible side reactions, with the additional advantage thatinclusion of the polyene monomer eliminates possible mercapto end groupswhich may lead to irreversible side reactions with the photochromicmaterials. The materials provided by this invention are also much morereadily tintable at relatively lower temperatures than opticalpolyurethane or polythiourethane resins; thus for incorporation ofphotochromic materials into the enhanced optical resin of this inventionthrough tinting, thermal transfer, or some other such technique,elevated temperatures, which may lead to serious degradation of manyphotochromic materials, are usually not required. The enhancedtintability of these optical materials may also lead to other advantagesover other materials for photochromic optical products.

The monomer mixture for casting or polymerization may be mixed togetherwith additives such as a lubricant, a mold releasing agent,polymerization initiator, catalyst, etc. preferably under non-reactingconditions, degassed and reacted using conventional techniques known inthe art.

It has been found that enhanced products are produced using thepreferred method of the invention.

Preferably, the active hydrogen containing monomer or, if two or moremonomers are used, they are mixed under non reaction conditions, usuallyroom temperature or below, and cooled to a temperature below about 15°C., preferably abut 5° C. The polyene monomer(s) and polyisocyanatemonomer(s) are mixed likewise under non reaction conditions usually atroom temperature or below and cooled to a temperature below about 15°C., preferably about 5° C. The two mixtures are combined at a lowtemperature and maintained at a temperature below about 15° C.,preferably 5° C. An initiator and a catalyst are added to promote thepolymerization. Also preferably added is an internal mold releasingagent to promote removal of the optical resin product from the castingmold after curing. The mixture is preferably degassed for 5-180 minutes,at a vacuum of preferably about 5 mmHg or less. The mixture is then keptin the mold and placed at a cool temperature preferably below 15° C. for0-72 hours and then cured at an elevated temperature. A preferred curingcycle is discussed below.

Since the monomer components may separate into two or more phases in themold using conventional procedures, the curing reaction between thecomponents may be allowed to proceed somewhat during mixing preferablyafter mixing of the active hydrogen group component or component mixtureand polyene-polyisocyanate mixture, so that the two components make up asingle uniform phase before pouring into the mold. While the liquidmixture is preferably degassed after mixing, bubbles may still form inthe mold depending on the type of monomers and the reaction conditions.In order to avoid such a phenomenon, it is necessary to conduct thepolymerization reaction while effecting sufficient heat removal andprecise temperature control. Although the reaction time and the reactiontemperature vary depending upon the combination of components, thepolymerization is generally carried out at −20° C. to 150° C. for 24 to72 hours. The hardness of the polymer resulting from the reactionreaches the maximum at a time where the polymerization reaction iscomplete and it does not increase beyond that maximum level. Thepolymerization may be stopped at or before the above-mentioned time orat any time as long as the resultant resin has the desired refractiveindex and Abbe number properties as an eyeglass lens or other opticproduct.

For the optic polymer system of the present invention it is preferredthat the following curing process be used in conjunction with thepreferred mixing process to provide a resin product having enhancedproperties. The mixture at a low temperature of preferably about 15° C.or lower is placed in the mold and is initially cured at a temperatureof about 0° C. to 60° C. The temperature is usually raised to this rangeover a period of up of 24 hours. The temperature is then raised over aperiod of about 1 to 32 hours to about 100 to 150° C., preferably 125°C. at a rate of about 0.1° C.-1° C. per minute, preferably 0.5° C.-0.15°C. per minute. The mixture is then maintained at about 125° C. for about4 to 32 hours, preferably 9-24 hours, at which point the temperature islowered over a period of about 1 to 32 hours to about 30° C., at a rateof about 0.05° C.-0.5° C., preferably 0.1° C., per minute.

A reaction catalyst is preferably employed in the process of theinvention to control the reaction rate. Any catalyst known in the art tobe suitable for use in producing polyurethanes and/or polythioethers maybe employed. Exemplary catalyst include tertiary amines and organo-tincompounds such as dibutyltindilaurate and tributylamine.

A radical initiator may be used in the process of the invention tocontrol the reaction rate for matching the formation of thioethermoieties with that of thiourethane moieties. Exemplary initiatorsinclude: 2,2′-Azobisisobutyronitrile,1,1′-Azobis(cyclohexanecarbonitrile),2,2′-azobis(2,4-dimethylvaleronitrile), azobis(methyl-isobutyrate),2,2′-azobis(2-methylbutyronitrile) and benzoyl peroxide.

An internal mold release agent (lubricant) is preferably incorporated inthe polymerization mixture for easier and better mold release of thepolymerized lens with the resulting lens having a higher profile ofregularity. Exemplary suitable internal mold release agents for use inthe present invention include: fluorine containing nonionic surfactants,alkyl quarternary ammonium salts, acid phosphate ester, higher fattyacid ester, fatty acid and silicon containing nonionic surfactants.

The optical resins of the present invention may also be formed as alinear polymer system for injection molding or compression moldingprocesses. Such linear polymer systems may be formed by polymerizing themixture of the monomers, preferably divinyl monomer, diisocyanate anddithiol in solution of a common solvent such as N,N-dimethyl-formamide(DMF) or in bulk. The reaction temperature is about 0-150° C. dependingon the monomer reactivity. Catalysts and initiators of amount of 10-5000ppm may be used in the mixture. The reaction time may be 1-72 hours. Theresulting terpolymer may be subjected to common purification process toeliminate unreacted monomers, solvents and other impurities.

The invention will be described by reference to the following exampleswhich are not intended to be limiting.

The physical properties of the polymer product of the subject inventionwere determined according to the following methods.

(1) Refractive Index: The refractive index was measured using a MetriconModel 2010 Prism Coupler at 20° C.

(2) Abbe Number: The Abbe number was measured using a Metricon Model2010 Prism Coupler at 20° C. according the following equation:$\upsilon_{d} = \frac{n_{D^{- 1}}}{n_{F} - n_{C}}$

where n_(D) is the refractive index determined at 589.3 nm, n_(F) is therefractive index determined at 486.1 nm, and n_(C) is the refractiveindex determined at 656.3 nm.

(3) Reaction Product is a Terpolymer and Not a Blend of Polymers: Thereaction products were examined with Nikon Optiphotz PolarisingMicroscope and no phase separation was observed. DSC (DifferentialScanning Colorimeter) measurement also shown that there is only singleT_(g).

(4) Shore D Hardness: The Shore D hardness was measured using HP-DRDurometer tester.

(5) Polymer Color: The color of the polymers was measured using BYKGardener Optical Spectrophotometer on polymer lenses.

(6) Tintability: The lenses were tinted using BPI® Molecular CatalyticBlack dye in a recommended concentration of water solution and followedby visual examination.

(7) Pencil Hardness: The pencil hardness was measured manually usingStaedtler Mars Lumograph pencils.

(8) Impact Resistance: According to the FDA standard, a steel ballhaving a diameter of 15.9 mm and a weight of 16.2 g was dropped in thecenter of a lens from a height of 127 cm. The impact resistance wasevaluated according to whether the lens was broken.

EXAMPLES Example 1

17.3 g (0.04 mol) of pentaerythritol tetrakis(2-mercaptoacetate), ascomponent A, was cooled to 5° C. 7.5 g (0.04 mol) of m-xylylenediisocyanate, as component B, and 7.75 g (0.022 mol) of pentaerythritoltetraacrylate, as component C, were mixed at room temperature and cooledto 0° C. They were combined at a temperature below 15° C. and themixture cooled to 0° C. 600 ppm of ZELEC UN mold releasing agent and0.02 g of 1,1′-azobis(cyclohexane-carbonitrile) and 60 ppm of dibutyltindilaurate were stirred into the mixture and the mixture degassed in 3mmHG vacuum for 1 hour. The mixture was maintained at about 15° C. Themixture was transferred into a mold composed of two curved glass platesand a rubber gasket. The filled mold was heated to 40° C. gradually over10 hours and the temperature was raised from 40° C. to 130° C. graduallyin 10 hours. The temperature was then maintained at 130° C. for 9 hoursand then decreased to room temperature gradually over 10 hours. The lenswas released easily from the mold. The resultant lens was colorless andhighly transparent and had a refractive index of 1.581, an Abbe's numberof 41, a Shore D Hardness of 91 and a pencil hardness of 1H. The gasketremained substantially unaffected. The lens was readily tinted with BPI®molecular catalytic black dye in a recommended concentration of watersolution at 60° C. over 8 minutes.

Examples 2-4

Using the same procedure as in Example 1, components A, B and Cdescribed in Table 1 were mixed with the same amount of mold releasingagent initiator and catalyst, degassed and filled into glass molds. Theywere then cured in the same manner. The results are shown in Table 1. InTable 1, the following abbreviations will be used:

1. PETMA for pentaerythritol tetrakis(2-mercaptoacetate)

2. PETA for pentaerythritol tetraacrylate

3. PETMP for pentaerythritol tetrakis(3-mercaptopropionate)

4. m-XDI for m-xylene diisocyanate

5. 1,2-EDT for 1,2-ethanedithiol

6. 2-MES for 2-mercaptoethyl sulfide

7. TATAT for triallyl-1,3,5-triazine-2,4,6(1H, 3H, 5H)-trione

Example 5

Into a 100 ml three-necked round bottom flask equipped with a droppingfunnel, a thermometer, a condenser, and a magnetic stirrer were added1.50 g (16 mmol) of 1,2-ethanedithiol and 6 g of dimethyl formamide(DMF). The solution was heated to 80° C. A room temperature solution of1.13 g (6 mmol) of m-xylylene diisocyanate in 2 g DMF was added dropwiseover 15 minutes and the temperature maintained at 80° C. After thereaction mixture was stirred for 1 hour at 80° C., 1.54 g (10 mmol) ofmethylene-bisacrylamide at 80° C. was added at one time. The reactionwas continued for 12 hours at about 90° C. The mixture was precipitatedin cold water and the polymer separated by filtration. The solidreaction product was a white powder after being dried in vacuum. Thepolymer has Tg of 110° C. and can be injection molded or compressionmolded into optical lenses which have a refractive index of 1.62 and anAbbe's number of 34.

COMPARATIVE EXAMPLES Comparative Examples 1-4

Using the same procedures as in Example 1, the indicated components aremixed with mold releasing agent, degassed and filled into glass moldsand cured in the same manner. The results are shown in Table 1.

TABLE 1 Refractive Reaction Example or Ratio of Index N²⁰ _(D) withComparative Component Component Component (-NCO + (Abbe Shore D PencilRubber External Example A B C Vinyl)/(-SH) Number) Tintability HardnessHardness Gasket Appearance Ex. 1 PETMA m-XDI PETA 1.05 1.580 (41) Verygood at 91 1H no colorless (0.04 mol) (0.04 mol) (0.02 mol) 60° C.transparent Ex. 2 PETMA m-XDI PETA 1.06 1.594 (40) Very good at 91 1H nocolorless (0.025 mol) (0.053 mol) (0.04 mol) 60° C. transparent 1,2 EDT(0.075 mol) Ex. 3 PETMP m-XDI PETA 1.06 1.588 (38) Very good at 85 — nocolorless (0.025) (0.053 mol) (0.040 mol) 60° C. transparent 2-MES(0.075 mol) Ex. 4 PETMA m-XDI TATAT 1.29 1.603 (36) Very good at 88 — nocolorless (0.028 mol) (0.084 mol) (0.064 mol) 60° C. transparent 1,2-EDT(0.084 mol) Comparative 2-MES m-XDI 1  1.62 (33) at 85° C. — — yesyellowish Ex. 1 (0.075 mol) (0.075) opaque (semi- crystalline)Comparative 1,2-EDT m-XDI 1  1.63 (31) at 85° C. — — yes yellowish Ex. 2(0.075 mol) (0.075 mol) opaque (semi- crystalline) Comparative PETMAm-XDI 1  1.61 (33) at 85° C. — — yes yellowish Ex. 3 (0.025 mol) (0.125mol) cloudy 1,2-EDT (0.075 mol) Comparative PETMA PETA 1  1.55 (49) Verygood at 90 1B no colorless Ex. 4 (0.04 mol) (0.04 mol) 60° C.transparent (with some deformation)

While the present invention has been particularly described, inconjunction with a specific preferred embodiment, it is evident thatmany alternatives, modifications and variations will be apparent tothose skilled in the art in light of the foregoing description. It istherefore contemplated that the appended claims will embrace any suchalternatives, modifications and variations as falling within the truescope and spirit of the present invention.

Thus, having described the invention, what is claimed is:
 1. A monomercomposition characterized by being curable and which is cured byreacting the composition at an elevated temperature to form ahomogeneous terpolymer resin of the monomer composition which terpolymerhas a single glass transition temperature, does not have any phaseseparation and is optically clear consisting essentially of: a firstmonomer represented by the formula: R(NCY)_(x)  wherein R is ahydrocarbon or substituted hydrocarbon radical, Y is oxygen or sulfurand x is two or more; a second polyene monomer wherein the polyenecontains only vinyl functional groups; and a third polythiol monomer. 2.The composition of claim 1 wherein Y is oxygen.
 3. The composition ofclaim 2 wherein the polyene is represented by the formula:[CH₂═CR₁—CO—A—]_(y) R₂ wherein R₁ is H or CH₃; A is oxygen, sulfur, orNH; R₂ is a polyvalent aliphatic, alicyclic or aromatic hydrocarbonresidue, and y is 2-6.
 4. The composition of claim 3 wherein thepolyisocyanate monomer is an aromatic diisocyanate.
 5. The compositionof claim 4 wherein the polyene monomer is a tri, or tetraacrylatecompound.
 6. The composition of claim 5 wherein the polythiol monomer isselected from the group consisting of a compound represented by theformula: HB—R3—(BH)_(z) wherein R₃ is an organic group selected from thegroup consisting of polyvalent aliphatic, alicyclic and aromatichydrocarbons, z is an integer of 1 to 3, and B is S; and

wherein R₄ is a substituted or unsubstituted aliphatic polyhydricalcohol residue, u is an integer of 1 or 2, and v is an integer of 2 to4.
 7. The composition of claim 6 wherein the polyisocyanate ism-xylylene diisocyanate, the polyene is pentaerythritol tetraacrylate,and the polythiol is selected from the group consisting ofpentaerythritol tetrakis(2-mercaptoacetate), 1,2-ethanedithiol andmixtures thereof.
 8. The composition of claim 1 wherein the polyene istriallyl-1,3,5-triazine-2,4,6(1H, 3H, 5H)-trione.
 9. A process formaking homogeneous terpolymer resins which terpolymers have a singleglass transition temperature, do not have any phase separation and whichare optically clear comprising reacting at an elevated temperature acurable composition consisting essentially of the composition ofclaim
 1. 10. The process of claim 9 wherein the monomers are admixedunder non-reactive conditions.
 11. The process of claim 9 wherein themonomers are admixed at a temperature of room temperature or below. 12.The process of claim 11 wherein an initiator and a reaction catalyst areadded to the composition.
 13. The process of claim 12 wherein theinitiator is 1,1′-azobis(cyclohexanecarbonitrile) and a reactioncatalyst is dibutyltindilaurate or tributylamine.
 14. The process ofclaim 9 wherein the composition is cured by heating the composition to afirst temperature of about 0° to 60° C., then heating the compositiongradually to a second temperature of about 100 to 150° C. over a periodof about 1 to 32 hours, maintaining the composition at the secondtemperature for about 4 to 32 hours, then cooling the composition to athird temperature of about 20 to 40° C. over a period of about 1 to 32hours.
 15. The composition of claim 1 wherein photochromic materials areused to provide a tinted optical product.
 16. The composition of claim15 wherein the photochromic materials are naphthopyran compounds, spirocompounds or indoline compounds.
 17. A terpolymer product made bypolymerizing the composition of claim
 1. 18. A polymer product made bypolymerizing the composition of claim 6.